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Book Review Photoinduced Electron Transfer. Parts AЦD. Edited by M. A. Fox and M. Chanon

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niques is concerned with digestion and extraction methods
for multielement analyses, the decomposition of organic matrices, and conventional methods such as acid digestion at
both atmospheric and high pressures; also discussed are sintering techniques, fusion with fluxes and microwave digestion. Special attention is given to digestion methods for geological samples.
The chapter on alternative techniques for sample introduction describes the capabilities of the hydride method and
of electrothermal vaporization, of the direct introduction of
powders in a gas jet- of techniques using suspensions, of
direct sample insertion and of spark ablation. In the chapter
on quantitative analysis by emission spectroscopy, methods
of calibration using synthetic standards, certified reference
materials, and standard addition are described. The meanings of the terms detection limit, determination limit and
precision are explained. In describing the various analytical
applications of ICP-OES, environmental analysis receives
relatively little attention, but this is compensated by the detailed discussions of development trends in on-line analysis,
automation of sample handling, etc.
The discussion of random and systematic errors is clear
and straightforward. The usual statistical test procedures are
described, as also is the importance of the spectral background and the methods used to measure it. The use of an
internal standard is not so necessary in ICP-OES as in arc
and spark emission spectroscopy, with which the author is
equally familiar, but nevertheless it can be useful in ICP-OES
for correcting fluctuations in the rate of sample introduction,
especially for high concentrations.
In the chapter on optimization of the operating variables,
the several different versions of the simplex procedures are
described. Here the author makes full use of the experience
gained from his own work, and presents this in a clearly
understandable form. A simple computer program for simplex optimization is also given.
The most complex problem encountered in the analysis of
real samples is that of interferences and the choice of suitable
emission lines. Nebulization interferences and matrix effects
arising from the plasma are briefly described. The relationship between interferences and optimization of variables is
discussed with regard to source power and height of observation. The analytical errors caused by background and interfering lines depend critically on the spectrometer resolution
achieved in practice. This dependence on resolution, although understood, is often complicated, and instead of
treating it in detail the reader is referred to relevant literature.
The chapter on combined techniques, in which ICP-OES
is coupled to various other analytical methods, describes in
particular the coupling to electrothermal vaporization and
the ICP-mass spectometry technique. The power of detection, the effects of other elements on the observed signals and
the spectral interferences which occur in ICP-MS for the
lighter elements are critically discussed.
The book is especially suitable as an introduction and
learning aid for practical ICP spectroscopy in the laboratory,
and it contains an adequate number of relevant literature
references for this purpose. For practical work it would perhaps also have been useful to include data on emission lines
commonly used in ICP-OES. The spectroscopic fundamentals can be found in the standard works by Boumans and
Monfaser. This book by Moore is likely to be of special
interest to technicians and geology students, since it contains
more of relevance for these groups than for environmental
analysts or users in the ultra-pure chemicals or biological
fields, a fact which is not surprising in view of the author’s
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own field of work. Thus, for example, there are no chapters
on the problems of trace analysis in relation to reagent purity
and purification, on working in dust-free environments, nor
on blanks and their relationship to ambient concentrations.
The book makes easy reading and has a pleasing format. It
will undoubtedly find a lot of use in the laboratory and in the
vicinity of the ICP spectrometer. For many newcomers to
ICP-OES as a modern multielement analytical technique it
will ease their introduction to the subject.
Jose A . C. Broekaert [NB 1036 IE]
Institut fiir Spektrochemie
Dortmund (FRG)
Photoinduced Electron Transfer. Parts A-D. Edited by M.A.
Fox and M . Chanon. Elsevier, Amsterdam 1988. Part A:
Conceptual Basis. xviii, 640 pp., DFI 360.00.--ISBN
0-444-871 22-5; Part B: Experimental Techniques and
Medium Effects. xviii, 748 pp., DFI 410.00.-ISBN 0444-871 23-3; Part C: Photoinduced Electron Transfer Reactions-Organic Substrates. xviii, 754 pp., DF1410.00.--ISBN 0-444-87124-1 ; Part D : Photoinduced Electron
Transfer Reactions-Inorganic
Substrates and Applications. xviii, 790 pp., DFI 425.00.-ISBN 0-444-871 25-X,
hardcover, set: DFI 1350.00.--ISBN 0-444-87121-7
The type of elementary reaction described as photoinduced electron transfer (PIET) has been studied both theoretically and, to a now increasing extent, experimentally.
One factor that has contributed to this considerable growth
of interest is the rapid progress achieved in the area of ultrafast techniques such as picosecond laser spectroscopy, which
provides remarkably short time resolution in studying the
dynamics of molecules and thereby of fast chemical processes. For the synthetic chemist the main significance of PIET
studies lies in the enticing prospect of gaining a better understanding of such reactions so as to be able to develop more
efficient catalytic and energy conversion processes; this is the
reason for the current attraction of this area of research.
M.A. Fox and M . Chanon, as editors of this very comprehensive work, have tried to bring together in four volumes as
many different aspects of this interdisciplinary fieid as possible. The 2600-page work consists of individual chapters in
the form of photographically reproduced manuscripts by 46
authors or author groups. Starting from an essentially theoretical conceptual basis (Vol. A), Vol. B deals with the experimental techniques and with medium effects, then Volumes C
and D describe actual examples in organic and inorganic
chemistry respectively, and some particular areas of application such as solar energy conversion and information storage.
In the excellent introductory chapter of Volume A M .
Chanon, M . D. Hawley and M . A. Fox give a general
overview of PIET processes and a clear account of the relevant physical quantities. This is followed by a very technically orientated chapter by J. P. Schermann, J P. Astruc, C.
Desfrangois and R. Barbe describing electron transfer between excited atoms and molecules. Some theoretical aspects
based on the Marcus equation are explained and discussed in
two articles by K. E Purcell and B. Blaive, and by M . R.
Wasielewski and E Wilkinson. The clear presentation by
D. C. Mauzerall of the problem of reverse electron transfer
deserves special mention. Another well-organized chapter is
that by G. Jones ZZ on the photochemistry and photophysics
of organic charge transfer complexes. Next come articles on
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exciplexes ( Y . Hans and 0. Anner), on the origin of solvent
effects ( D . E Cukf), and on the photochemistry of organic
free radicals, cations and anions ( J . Eriksen). Finally, M .
Chanon and L. Eberson discuss in detail the fascinating phenomenon of photoinduced chain reactions; a highlight of
this is a very useful compilation of frequently used components and sensitized electron transfer reactions.
Part B begins with a status report by J. A. Deluire and .
I
FuurP on laser spectroscopic methods; the development of
nanosecond, picosecond and even femtosecond pulsed lasers
for studying transient species is described. Two articles on
the application of pulse radiolysis to inorganic reactions to
generate short-lived species, by K L. Waltz and by P. Neta
and A. Hurriman, are followed by a discussion of organic
systems. arranged according to classes of organic compounds, with special emphasis on porphyrins and redox catalysts. These chapters illustrate the complex character of
photolysis and radiolysis as applied to understanding intraand intermolecular electron transfer processes. S. G. Boxer,
R . A. Goldstein and S. Franzen describe how reaction dynamics can be influenced by applying magnetic and electric
fields. Here the reader is first introduced to the theory of
CIDNP and its application to the photosynthetic reaction
center and to other organic donor-acceptor systems. A comparison between photoconductivity and the processes occurring in the photosynthetic reaction center serves to illustrate
the effects of electric fields on PIET reactions. Next comes a
lengthy article in which M . Julliurd surveys the various classical methods and experiments for detecting PIET reactions.
A large number of studies on donor-acceptor systems are
cited and tabulated according to the criteria used in the investigations. Using various experimental data as examples,
the reader is made aware not only of the methods and criteria
for proving the occurrence of a PIET, but also of the difficulties and possible sources of error. L. Brus describes studies of electron transfer reactions based on measuring inelastic scattering of photons by transient species (time-resolved
resonance Raman spectroscopy). In particular, applications
to studying homogeneous reactions in liquids and heterogeneous electron transfer at semiconductor-electrolyte interFaces are discussed. L. Kevun describes the use ofconventional ESR spectroscopy as well as modern double resonance
(ENDOR) and electron spin-echo modulation (ESEM) techniques for the identification of paramagnetic intermediates.
The advantages of the ESEM method for characterizing heterogeneous structures (semiconductors, micelles, vesicles)
are clearly pointed out. Next J. E. Baggott, C. H . Lundord
and C. Morulejo, and in a separate article A . D . Kirk, describe temperature, wavelength and pressure effects in PIET
reactions from a mechanistic point of view. It appears that
there are still uncertainties about some aspects, in particular
the interpretation of activation volumes, where the theory is
not yet well developed.
In Part 2 of Volume B, J. Suntamaria begins with a lucid
treatment of solvent and salt effects on energetics and kinetics. S. Bural and J. H. Fendler provide a link from this to
PIET reactions in “organized” media, which range from
mimetic vesicles and lipid bilayer membranes to biological
systems. After an introduction to the preparation of organizates of this kind, they give an interesting account of some
recent PIET experiments. The article also discusses the stabilization of semiconducting colloids in organizates and their
potential application in redox catalysis.
S . Nukabuyushi and 7: Kuwui extend this connection further to electron transfer processes at semiconductor interfaces, which are important in relation to photoelectrodes,
photocatalysis and sensitization. The theory of PIET
Anxeu. ChiJtn. h 1 . Ed. Engl. 29 (1990) Nu. 6
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through boundary layers is described, as well as spectroscopic analysis, electron transfer dynamics and the design of such
materials. J. Rabani provides a lucid account of how PIET
processes can be influenced by polyelectrolytes. Carefully
controlled tailoring of polymers by incorporating donors,
acceptors or sensitizers can result in a slowing down of the
reverse electron transfer process which presents a serious
problem in photochemical systems for energy conversion
and storage. This article is very topical, and the presentation
is clear and comprehensible.
In Part C (PIET in organic and biochemical substrates),
E D. Lewis begins by reporting on electron transfer reactions
in compounds with multiple CC bonds. He succeeds In classifying the many different ways in which olefinic radical
cations and anions can react. P. G. Gussman gives an excellent introduction and review of PIET reactions of strained
hydrocarbons. The clear presentation and logical structure
give the reader an insight into what the author describes at
the end of the article as a “fascinating area of photochemistry”. A. Albini and A . Sulpizio classify the PIET reactions
of arenes according to their reaction mechanisms, i.e. the
subsequent reactions of the radical species produced. Unfortunately, the authors give hardly any information about the
photoinduced S,,1 reactions of arenes, justifying this by the
fact that review articles already exist (although these were
published in 1983 or earlier). An update on this topic would
have been appropriate. Next A. Luhlache-Combier, in a contribution of nearly 180 pages, extends the S,,1 concept to the
synthesis of heteroarenes and to their subsequent reactions.
Numerous physical-chemical relationships are introduced,
so that the combination of synthetic aspects with photochemical data provides the reader with a clear idea of the
advantages and difficulties of such reactions. The following
article, by M . Hoshino and H . Shizuka, gives a very explicit
account, supported by a few examples, of the photophysics
and photochemistry of aromatic carbonyl compounds. Also
clearly written is the chapter by P. S. Muriano on photochemical reactions of iminium ions. The redder interested in
synthetic aspects will certainly profit from the application of
such reactions to complex systems such as alkaloids and
condensed heterocycles. N . J. Pienta gives a general survey of
the photochemistry of amines, thiols and thioethers (with
300 references). The article includes informative comparisons with other chemical and electrochemical methods for
generating reactive radical cations. Well arranged tables are
provided which also cover biochemical, inorganic, organometallic and polymeric systems. The chapter by u! R. Bowman is devoted entirely to photoinduced nucleophilic substitutions at sp3 carbon atoms. Numerous examples, arranged
according to substrates, leaving groups, nucleophiles and
mechanisms, give the reader an idea of the applicability of
these reactions and their limitations. X . Ci and D. G. Whitten
adopt a mechanistic viewpoint in discussing photoreductions
using tertiary amines as donors, and photoinduced redox
fragmentations of aminoalcohols. Part C ends with two
chapters by S. Fukuzumi and 7: Tanaku which deal in a clear,
precise and comprehensive way with the (photoinduced) redox chemistry of biological systems, which are covered
rather too scantily in the work as a whole; the examples
described here are the 1,4-dihydropyridines NAD(P)H and
the flavines. The reader is given an excellent and informative
introduction to the redox properties of these compounds in
the ground and excited states, followed by a detailed discussion of their PIET reactions. In making it easier to understand complicated photocatalytic cycles in systems analogous to that of photosynthesis, this article offers much
more than a mere introductory survey.
Verlu.~.sge.sellsthajl
mbH, 0-6940 Weinheim. 1990
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Volume D begins with a concise summary by M . A . Fox of
0, activation by PIET, which again is of biological importance. The following chapter by H. R. Macke and A. E
Williamson transition metal complexes of 0, is unfortunately too brief and conventional in content. In somewhat
greater detail N. Serpone describes PIET reactions of classical hexacoordinated complexes, in particular those containing polypyridyl ligands. PIET reactions occur, often unexpectedly, in weakly interacting systems such as ion pair
complexes or “supramolecular” complexes ; these highly
topical reactions are described by K Balzini and E Scandola.
This is followed by a short chapter in which A. Vogler describes the intramolecular electron transfer between weakly
coupled redox centers, e.g. in multinuclear complexes. The
chapter by C. Giannotti, S. Gaspard and P. Krausz on PIET
in organometallic transition metal compounds is disappointing, not just because of the poor visual impression given by
the typescript, but due to the fact that essentially all that it
contains is a compiIation of results on cyano complexes together with a few metallocenes and carbonyl complexes.
Readers interested in this topic are better served by the recent
monographs by Kochi or by Hennig and Rehorek.
The final chapter of Volume D contains articles on the
actual and potential applications of PIET. On the basis of
well documented examples, R. Pichat and M . A. Fox describe photochemical “catalysis” at semiconductor surfaces.
Semiconductors are also at the center of the article by M .
Griitzel on solar energy applications. Also related to this
theme, J. S. Connolly and J R. Bolton have put together a
comprehensive “historical” account of the attempts at producing artificial photosynthesis, but it is not easy reading
except for insiders. The following articles, on the importance
of PIET in polymerization initiation reactions ( Y Shirota), in
the processing and storage of information ( M . K Alfiinov
and K A. Sazhnikov), in modern photoresist technology, ( E
Schue, L. Giral, C. Montiginoul and B. Serre), and in phototoxicity, either involving or not involving 0, ( N . Paillous and
M . Comtat),each give only a brief insight into areas of application where the PIET concept has already proved its usefulness.
At the end of Volume D, in addition to a large subject
index, there is a very long and comprehensive author index
(137 pp.) for the collected literature citations in all the articles. It would have been equally useful to have included,
along with these pages reminiscent of the Science Citation
Index, a list of the most important commonly used
acronyms; the lack of such a list means that many of the
articles make difficult reading if one is unprepared. With
such a large number of authors and a field of a very interdisciplinary nature, it is probably unavoidable that some basic
concepts, some frequently used experimental techniques and
some particularly relevant chemical systems are described
several times. In some respects this is an advantage from the
reader’s standpoint, since there are inevitably variations in
the quality and comprehensiveness of the articles with such
a heterogeneous team of authors. Nevertheless, we must notice that, despite the claim regarding comprehensive coverage, two important topics receive rather too little attention,
namely PIET processes in organometallic chemistry and in
biochemistry.
And now to what is undoubtedly a negative aspect of the
work: the price of the four volumes! For a work in this price
range the photographic reproduction of 47 typescripts in
different formats, with the poor visual impression that this
gives, is quite unacceptable. Consequently one can predict,
regretfully, that although this is on the whole a very useful
collection of articles on a subject of high topicality, the wide
readership which is desirable will not be realized in practice.
Peter Biiuerle [NB 1012 IE]
Institut fur Organische Chemie
der Universitat Stuttgart
Wolfgang Kaim
Institut fur Anorgdnische Chemie
der Universitat Stuttgart (FRG)
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